Effect of Anion Species on Ion Current Rectification Properties of Positively Charged Nanochannels

Biological ion channels can realize delicate mass transport under complicated physiological conditions. Artificial nanochannels can achieve biomimetic ion current rectification (ICR), gating, and selectivity that are mostly performed in pure salt solutions. Synthetic nanochannels that can function under mixed ion systems are highly desirable, yet their performances are hard to be compared to those under pure systems. Seeking out the potential reasons by investigating the effect of mixed-system components on the ion-transport properties of the constructed nanochannels seems necessary and important. Herein, we report the effect of anions with different charges and sizes on the ICR properties of positively charged nanochannels. Among the investigated anions, the low-valent anions showed no impact on the ICR direction, while the high-valent component ferrocyanide [Fe(CN)₆^4-] caused significant ICR inversion. The ICR inversion mechanism is evidenced to result from the adsorption of Fe(CN)₆^4--induced surface charge reversal, which relates to solution concentration, pH conditions, and nanochannel sizes and applies to both aminated and quaternized nanochannels that are positively charged. Noticeably, Fe(CN)₆^4- is found to interfere with the transport of protein molecules in the nanochannel. This work points out that the ion species from mixed systems would potentially impact the intrinsic ICR properties of the nanochannels. Replacing highly charged counterions with organic components would be promising in building up future nanochannel-based mass transport systems running under mixed systems.